The present invention relates to a porous honeycomb filter and a manufacturing method thereof, and more particularly to a porous honeycomb filter that has a high efficiency in collecting fine particles (particulates) and the like. This porous honeycomb filter can prevent an increase in pressure loss due to the plugging of pores, and it is especially suitable for exploiting the characteristics thereof for diesel engines that use recent high-pressure fuel injection, common rails, etc. The invention also relates to a manufacturing method thereof.
Porous honeycomb filters, having a structure in which a plurality of through holes opened to the end surface of the exhaust gas flow-in side and to the end surface of the exhaust gas flow-out side are alternately sealed at both the end surfaces, have recently been used as apparatuses for removing particulate in exhaust gas. In these porous honeycomb filters the exhaust gas that flows in at the exhaust gas flow-in side end surface is forced to pass through partition walls (having a plurality of pores) between through holes to thereby collect and remove particulate in exhaust gas.
In this porous honeycomb filter, the pore distribution needs to be controlled because performance figures such as collection efficiency and pressure loss vary depending on the diameter of the pores formed on partition walls between through holes in relation to the size of particulates in the exhaust gas.
Traditionally, a porous honeycomb filter made from cordierite, which is excellent in heat resistance, or from silicon carbide, which is frequently used. For porous honeycomb filters made from silicon carbide, of which pore diameter is easily controlled, a filter with an average pore diameter of 1 to 15 xcexcm and the pore diameter thereof being controlled with the standard deviation (SD) of as extremely narrow a range as 0.20 or less in the pore distribution, has been disclosed (JP-A-5-23512).
On the other hand, for porous honeycomb filters made from cordierite where the pore diameter is controlled, a honeycomb filter has been disclosed with an average pore diameter of 25 to 40 xcexcm. It is obtained by a manufacturing method in which the porosity is increased by not causing kaolin and aluminum oxide to be contained in the cordierite-forming raw material and also by using a raw material made by adding a specified organic blowing agent or a flammable substance to a cordierite raw material. The cordierite raw material is composed of aluminium hydroxide (the powders with particle diameters of 0.5 to 3 xcexcm and of 5 to 15 xcexcm make up 50 to 100% of the whole of the aluminium hydroxide), fused silica (average particle diameter of 30 to 100 xcexcm) and talc, of which particle diameter is controlled within a specified range, has been disclosed (JP-A-9-77573).
However, in this honeycomb filter, the pore diameter thereof is primarily controlled by aluminium hydroxide and an organic blowing agent or a flammable substance, and so the average pore diameter was capable of being controlled, but the pore distribution was not capable of being set in a desired narrow range. In addition, the aluminium hydroxide was made to become coarse particles, thereby causing the problem of increasing the coefficient of thermal expansion as well.
To the contrary, honeycomb filters made by a manufacturing method in which a raw material prepared by adding graphite as a pore-forming agent to a cordierite-forming raw material produced by making each component of talc, silica, alumina and kaolin a powder of a specific particle diameter and then mixing them in specific contents, with pore distributions in which  less than 1 greater than  the pores with a diameter of 2 xcexcm or less makes up 7% by volume or less of the total pore volume, and  less than 2 greater than  the pores with a diameter of 100 xcexcm or more makes up 10% by volume or less of the total pore volume have been disclosed, respectively, in Japanese Patent Nos. 2578176 and 2726616.
In these honeycomb filters, however, the difference in easiness of controlling the pore diameter for each component was not taken into consideration, and therefore the lower limit or the upper limit of the pore distribution was only controlled at most and it was impossible to set the pore distribution in a desired narrow range.
To the contrary, a honeycomb filter where a pore with pore diameters of 10 to 50 xcexcm makes up 52.0 to 74.1% by volume of the total pores, is obtained by a manufacturing method in which, focusing on the difference in easiness of controlling the pore diameter for each component of talc, silica, alumina and kaolin, a cordierite-forming raw material is prepared by setting the powder with a particle diameter of 150 xcexcm or more to be 3% by weight or less of the whole raw material and also setting the powder with a particle diameter of 45 xcexcm or less to be 25% by weight or less, for both talc and silica, has been proposed (JP-A-7-38930).
In this honeycomb filter, the pore diameter thereof is controlled in a narrow range of from 10 to 50 xcexcm for the first time in a honeycomb filter made from cordierite. Compared with a variety of cordierite honeycomb filters mentioned above, the filter can not only increase collection efficiency, but also prevents an increase in pressure loss by the prevention of plugging. In addition, the filter can lower the coefficient of thermal expansion by decreasing the particle diameter of the talc contained in the filter.
However, particulates in exhaust gas have lately been made small and been homogenized (particle diameter of particulates is almost about 1 xcexcm) with decreasing emission as a result of improved diesel engines (high-pressure fuel injection, common rails, etc. are used), and thus a honeycomb filter in which the pore diameter is extremely highly controlled has been strongly required.
On the contrary, while the aforementioned honeycomb filter has been produced, completely neglecting a close association of kaolin in a cordierite-forming raw material with the formation of a pore of 10 xcexcm or less, pores with a diameter of 10 to 50 xcexcm cannot be formed at a high level of 75.0% by volume or more, so that recent demand cannot be satisfied.
The present invention has been made considering the aforementioned problem, and the objects thereof are to provide a porous honeycomb filter that has a high efficiency in collecting fine particles (particulates) and the like and prevents an increase in pressure loss due to the plugging of the pores, especially suitable for exploiting these characteristics for diesel engines that use recent high-pressure fuel injection, common rails, etc., and also to provide a manufacturing method thereof.
The inventors, as a result of studies to solve the aforementioned problem, have found out that the pore size distribution can be highly controlled in a desired range by regulating the particle diameter of the silica component of a cordierite-forming raw material and also lowering the concentration of the kaolin, and have completed the present invention.
In other words, the present invention provides a porous honeycomb filter made from a raw material composed of cordierite as the primary crystalline phase, of which the pore distribution is controlled, characterized in that, in the pore distribution, the volume of a pore with a diameter of less than 10 xcexcm is 15% or less of the total pore volume, the volume of a pore with a diameter of 10 to 50 xcexcm is 75% or more of the total pore volume, and the volume of a pore with a diameter of above 50 xcexcm is 10% or less of the total pore volume.
In a honeycomb filter of the present invention, the porosity of the honeycomb filter is preferably 50 to 75%, more preferably 65 to 75%, and particularly preferably 68 to 75%. In addition, the coefficient of thermal expansion of the honeycomb filter is preferably 1.0xc3x9710xe2x88x926/xc2x0 C. or less at 40 to 800xc2x0 C.
Further, the present invention provides a method of manufacturing a porous honeycomb filter, using a ceramic raw material primarily composed of a cordierite-forming raw material, in which the cordierite-forming raw material contains 10% by weight or less of kaolin and also has a particle size distribution in which the raw material contains 1% by weight or less of a powder with a particle diameter of 75 xcexcm or more of silica (SiO2) source components except both kaolin and talc.
In the method of manufacturing a honeycomb filter of the present invention, the filter can contain 1 to 10% by weight of kaolin, in contrast to the manufacturing method described in Japanese Patent Laid-Open 9-77573.
In addition, silica (SiO2) source components except both kaolin and talc preferably contain at least one species of quartz and fused silica.
Furthermore, a cordierite-forming raw material preferably contains as alumina (Al2O3) source components at least one species of aluminium oxide and aluminium hydroxide. In this case, the raw material preferably contains as alumina (Al2O3) source components 15 to 45% by weight of aluminium hydroxide with a particle diameter of 1 to 10 xcexcm, or 0 to 20% by weight of aluminium oxide with a particle diameter of from 4 to 8 xcexcm.
Additionally, a cordierite-forming raw material preferably contains 37 to 40% by weight of talc as a magnesia (MgO) source component. In this case, the particle diameter of the talc is preferably 5 to 40 xcexcm.
Further, a ceramic raw material preferably contains 1 to 4 parts by weight of foam resin with respect to 100 parts by weight of a cordierite-forming raw material.
Embodiments of the present invention will be described in detail in the following.
1. Porous Honeycomb Filter
A porous honeycomb filter of the present invention is a porous honeycomb filter made from cordierite as the primary crystalline phase, of which pore distribution is highly controlled in a specified range.
A detailed description will be given in the following.
A porous honeycomb filter of the present invention is made from cordierite as the primary crystal and the cordierite may be selected from any one form of oriented, unoriented, xcex1 crystalline, and xcex2 crystalline forms, and the like.
In addition, the filter may contain other crystalline phases, including mullite, zircon, aluminium titanate, clay bond silicon carbide, zirconia, spinel, indialite, sapphirine, corundum and titania.
Further, these crystalline phases may be contained as a single species or as two or more species at the same time.
In the pore distribution of a porous honeycomb filter of the present invention, the volume of a pore with a diameter of below 10 xcexcm is 15% or less of the total pore volume, the volume of a pore with a diameter of 10 to 50 xcexcm is 75 to 100% of the total pore volume, and the volume of a pore with a diameter of above 50 xcexcm is 10% or less of the total pore volume.
When the volume of a pore with a diameter of 10 to 50 xcexcm comes to be less than 75% of the total pore volume and the volume of a pore with a diameter of below 10 xcexcm exceeds 15% of the total pore volume, a pressure loss is increased due to the plugging of pores. Further, when a catalyst is made to attach to the filter, a pressure loss is increased due to plugging of pores caused by the catalyst. On the other hand, when the volume of a pore with a diameter of 10 to 50 xcexcm comes to be less than 75% of the total pore volume and the volume of a pore with a diameter of above 50 xcexcm exceeds 10% of the total pore volume, the efficiency in collecting particulates is decreased.
In particular, since particulates are made small and homogenized as a result of recent improved diesel engines, it is difficult to increase the collection efficiency for particulates in line with such improvement in diesel engines, unless the volume of a pore with a diameter of 10 to 50 xcexcm is as high as 75% or more of the total pore volume for high efficiency.
In a honeycomb filter of the present invention, from the viewpoint of decreasing pressure loss and increasing collection efficiency, the porosity is preferably 50 to 75%, more preferably from 65 to 75% and particularly preferably 68 to 75%. In addition, in terms of improving thermal shock resistance when in use at high temperature, the coefficient of thermal expansion is preferably 1.0xc3x9710xe2x88x926/xc2x0 C. or less at 40 to 800xc2x0 C.
Although a honeycomb filter of the present invention normally has a structure in which a plurality of through holes opened to the end surface of the exhaust gas flow-in side and to the end surface of the exhaust gas flow-out side are alternately sealed at both the end surfaces, the shape of the honeycomb filter is not particularly restricted. For example, the filter may be a cylinder having end surfaces with a shape of a circle or an ellipse, a prism having the end surfaces with a shape of a polygon such as a triangle or a square, a shape in which the sides of these cylinder and prism are bent like an xe2x80x9cdoglegged shape,xe2x80x9d or the like. In addition, the shape of through holes is not particularly limited. For example, the sectional shape may be a polygon such as a square or an octagon, a circle, an ellipse, or the like.
Furthermore, a porous honeycomb filter of the present invention can be manufactured by a method described below, or the like.
2. A Method of Manufacturing a Porous Honeycomb Filter
A method of manufacturing a porous honeycomb filter of the present invention is a method of manufacturing a porous honeycomb filter using a ceramic raw material made from a primary raw material of a cordierite-forming raw material, in which the contents and particle diameters of specific components in a cordierite-forming raw material are controlled in specified ranges.
Detailed descriptions will be given in the following.
A cordierite-forming raw material used in the present invention has a particle size distribution in which the raw material contains 1% by weight or less of a powder with a particle diameter of 75 xcexcm or more of silica (SiO2) source components except both kaolin and talc, or more preferably 0.5% by weight or less.
As a result, pores with a narrow diameter range of 10 to 50 xcexcm can be formed in an extremely high yield and a honeycomb filter having a high collection efficiency and exhibiting no increase in pressure loss due to plugging of pores can be manufactured.
In other words, the present invention has found out that silica (SiO2) source components except both kaolin and talc in a cordierite-forming raw material, which are different from other components, can form pores of diameters substantially corresponding to the particle sizes of components, and that, noticing that the silica source components rarely participate in forming a pore with a diameter of 10 xcexcm or less, pores with a narrow diameter range of 10 to 50 xcexcm can be formed in an extremely high yield by removing a coarse powder with a diameter of 75 xcexcm or more.
Silica (SiO2) source components except both kaolin and talc include quartz, fused silica and mullite. Of them, at least one species of quartz and fused silica is preferably contained because they stably exist to high temperature during firing and pore diameters thereof are easily controlled.
A cordierite-forming raw material preferably contains 15 to 20% by weight of these silica (SiO2) source components. In addition, Na2O, K2O, etc. may be contained as impurities, and the total content of these impurities in silica (SiO2) source components is preferably 0.01% by weight or less because containing these impurities can prevent an increase in the coefficient of thermal expansion.
A cordierite-forming raw material used in the present invention should further contain 10% by weight or less of kaolin.
When the content of kaolin exceeds 10% by weight, the formation of a pore with a diameter of less than 10 xcexcm cannot be controlled, so that it becomes impossible to set the volume of a pore with a diameter of from 10 to 50 xcexcm to be 75% or more of the total pore volume even though the particle sizes of the aforementioned silica (SiO2) source components except both kaolin and talc are controlled.
That is, in the present invention, in addition to the control of the particle size distribution of the aforementioned silica (SiO2) source components, noticing that the kaolin in a cordierite-forming raw material mainly participates in forming a pore with a diameter of less than 10 xcexcm, the formation of the pore with a diameter of less than 10 xcexcm has been found to be able to be almost controlled by decreasing the content of kaolin to 10% by weight or less.
Additionally, in the present invent, since the content of kaolin is constrained by controlling the pore distribution, kaolin may be contained in the range of from 1 to 10% by weight, in contrast to the manufacturing method described in JP-A-9-77573.
In addition, although kaolin may contain mica, quartz, etc. as impurities, containing these impurities can prevent an increase in the coefficient of thermal expansion, and so the content is preferably 2% by weight or less.
Because each component for a cordierite-forming raw material used in the present invention is formulated to prepare a cordierite crystal with a theoretical composition, in addition to both the aforementioned silica (SiO2) source components and kaolin, for example, magnesia (MgO) source components such as talc and alumina (Al2O3) source components such as aluminium oxide and aluminium hydroxide need to be formulated.
As alumina (Al2O3) source components, one or both species of aluminium oxide and aluminium hydroxide, which have few impurities, are preferably contained, and particularly aluminium hydroxide is preferably contained.
In addition, some particle sizes of alumina (Al2O3) source components can lower the coefficient of thermal expansion and also can precisely control the pore size distribution by means of the particle size distribution of the aforementioned silica (SiO2) source components, and thus the particle diameter of aluminium hydroxide is preferably 1 to 10 xcexcm and the particle diameter of aluminium oxide is preferably 4 to 8 xcexcm.
Furthermore, for alumina (Al2O3) source components, a cordierite-forming raw material preferably contains 15 to 45% by weight of aluminium hydroxide and preferably contains 0 to 20% by weight of aluminium oxide.
Magnesia (MgO) source components, for example, include talc and magnesite and particularly talc is preferably contained. A cordierite-forming raw material preferably contains 37 to 40% by weight of talc. The particle diameter of talc, which lowers the coefficient of thermal expansion, is preferably 5 to 40 xcexcm, more preferably 10 to 30 xcexcm.
In addition, magnesia (MgO) source components such as talc used in the present invention may contain impurities, including Fe2O3, CaO, Na2O and K2O.
However, the content of Fe2O3 in magnesia (MgO) source components is preferably 0.1 to 2.5% by weight. A content in this range can lower the coefficient of thermal expansion and can also provide a high porosity.
In addition, containing CaO, Na2O and K2O lowers the coefficient of thermal expansion, and so the total content thereof in magnesia (MgO) source components is preferably 0.35% by weight or less.
The manufacturing method of the present invention can increase collection efficiency and also decrease pressure loss by further increasing porosity, and thus a cordierite-forming raw material preferably contains as an additive a pore-forming agent, or the like for forming pores.
Pore-forming agents, for example, include foam resins such as acrylic microcapsules, graphite, flour, starch, phenolic resin, poly(methyl methacrylate), polyethylene, and poly(ethylene terephthalate) and expanded foam resins such as acrylic microcapsules are preferable.
Expanded foam resins such as acrylic microcapsules are hollow and thus can, in a few amount, provide a honeycomb filter of a high porosity and can restrain heat liberation of a pore-forming material in a firing step, thereby lowering heat liberation in the firing step and decreasing generation of thermal stress even when a honeycomb filter of a high porosity is prepared by adding a pore-forming material.
Of course, although addition of a large amount of foam resin makes the porosity of an obtained honeycomb filter extremely large, the intensity is decreased to cause the filter to be easily damaged during canning, or the like. Accordingly, the content of foam resin is preferably 1.0 to 4.0 parts by weight with respect to 100 parts by weight of a cordierite-forming raw material, more preferably 1.5 to 3.0 parts by weight.
In the present invention, as necessary, other additives can be contained; for example, a binder or a dispersant for promoting the dispersion into the medium of fluid may be contained.
In addition, a binder includes hydroxypropylmethyl cellulose, methyl cellulose, hydroxyethyl cellulose, carboxylmethyl cellulose, or polyvinyl alcohol; a dispersant includes ethylene glycol, dextrin, fatty acid soap, or polyalcohol.
Further, each additive described above can be used singly or in combination of two species or more, depending on purpose.
In the present invention, nothing is limited except that the contents and particle diameters of particular components in a cordierite-forming raw material are controlled in specified ranges. For example, a honeycomb filter can be produced in the following manufacturing process.
First, with respect to 100 parts by weight of the aforementioned cordierite-forming raw material, 3 to 5 parts by weight of a binder, 2 to 40 parts by weight of a pore-forming agent, 0.5 to 2 parts by weight of dispersant, and 10 to 40 parts by weight of water are charged and then kneaded, and the compound is plasticized.
Second, molding of a raw material to be plasticized can be carried out by means of the extrusion method; the injection molding method; the compression molding method; a method in which after a ceramic raw material is molded in a cylindrical shape, the through hole is molded; or the like. Of them, the extrusion method, which easily permits continuous molding and causes a cordierite crystal to be oriented leading to low thermal expansion coefficient, is preferably used.
Third, drying of a raw molded article can be carried out by hot-air drying, microwave drying, dielectric drying, reduced-pressure drying, vacuum drying, freezing drying, or the like. Of them, a drying step of a combination of hot-air drying and microwave drying or of hot-air drying and dielectric drying is preferable in terms of being able to dry the whole rapidly and homogeneously.
Finally, firing of a dried molded article, although depending on the size of the dried molded article, is normally conducted preferably at a temperature of 1410 to 1440xc2x0 C. for 3 to 7 hours. In addition, the drying step and the firing step may be conducted continuously.
Examples of the present invention will be described in detail in the following. However, the present invention is not limited to the examples.
1. Evaluation Method
Honeycomb filters obtained in the examples and comparative examples described later were evaluated by the following methods.
(1) Pore Distribution and Average Diameter of Pores
Pore distributions and average diameters of pores were measured by a mercury injection porosimeter manufactured by Micromeritics Corporation.
(2) Porosity
Porosity was calculated from the total pore volume, regarding the absolute specific gravity of cordierite as 2.52 g/cc.
(3) Collection Efficiency
Exhaust gas with soot generated by a soot generator was passed through a honeycomb filter prepared in each example or comparative example for a constant time (2 minutes). After filtration, the soot contained in the exhaust gas was collected with a filter paper and then the weight (W1) of the soot was measured. Also, exhaust gas with soot generated for the same time was collected with a filter paper without being passed through a filter and then the weight (W2) of the soot was measured. Thus obtained weights (W1 and W2) were substituted in the equation (1) below to evaluate collection efficiencies.
(W2xe2x88x92W1)/(W2)xc3x97100xe2x80x83xe2x80x83(1)
(4) Soot Collection Pressure Loss
First, to both end surfaces of a honeycomb filter obtained in each example or comparative example was pressed against a ring with an inside diameter xcfx86 of 130 mm and soot generated by a soot generator through this ring was flowed within the range of 130 mm xcfx86 of the honeycomb filter to collect 10 g of soot.
Finally, air of 2.27 Nm3/min was flowed, with the soot collected on honeycomb filter, and then the pressure difference upstream and downstream the filter was measured to evaluate the pressure loss in a state in which the soot is collected.